Detergent bar



United States Patent O 3,291,744 DETERGENT BAR James Calvin Bohrer, East Brunswick, N.J., assignor to Colgate-Palmolive Company, New York, N.Y., a corporation of Delaware N Drawing. Filed July 12, 1965, Ser. No. 471,425 9 Claims. Cl. 252161) This application is a continuation-in-part of applications Ser. No. 848,565, filed October 26, 1959, now abandoned, and Ser. No. 264,039, filed March 11, 1965, now abandoned.

This invention relates to a synthetic detergent bar which has the excellent washing properties characteristic of the synthetic detergents :but unlike many synthetic detergent compositions, can be milled, plodded and pressed on soap-making equipment and possesses many of the more desirable product characteristics of soaps. More particularly, this invention is of a detergent bar comprising a minor portion of a straight chain alkyl aryl sulfonate and a major portion of a normal alkyl sulfonate of specified chemical structure as hereinafter described.

In recent years significant progress has been made in the production of bar and cake detergents based on synthetic organic detersive materials. Combinations of such detergents have been made and some of these combinations have been found to possess properties which make them useful for the manufacture of detergent bars. The ordinary higher fatty acid soaps have been blended with synthetic organic detergents and some of these combination soap-synthetic compositions have had the Washing properties characteristic of synthetic detergents while still possessing several favorable properties of the soap. In the manufacture of particulate detergent products, as distinguished from detergent bars, the physical characteristics of the detergent composition are not as critical, as a rule, because such detrimental properties as tackiness, hygroscopicity and softness, among others, either are not of great importance in making an acceptable product or can be eliminated or obscured by the addition of builders, fillers or other suitable agents. In part the tolerance of these powder formulations for such synthetic detergents is attributable to the absence of a necessity of converting the detergent composition to a special physical form. In the manufacture of detergent bars however, the final shape, appearance, cohesiveness and solubility properties of the product are of great importance and may substantialy afiect its marketability Because detergent compositions should be milled, plodded and pressed to obtain a bar of satisfactory appearance and physical structure these compositions have to be of such properties that they can be worked and shaped readily. Unlike the fatty acid soaps, most synthetic detergents are difficult to process without the incorporation therein of various fillers and/ or plasticizers which counteract the adverse characteristics of the detergent. Unfortunately, for the production of a detergent product of highest quality the employment of fillers, builders and certain plasticizers should be avoided. Thus, an object of the extensive research work which has been undertaken in this field is to discover synthetic organic detergents which have suitable product and processing characteristics by themselves and therefore do not require non-detergent additives to make a suitable bar product.

3,291,744 Patented Dec. 13, 1966 As a result of the search for detergents superior in washing properties to soap but equivalent or better than soap in their physical characteristics, such as hardness, plasticity under pressure, workability, extrusion, film formation, solubility rate, little sloughing, rehardening after moi'stening, gloss and tactile properties, to mention some, it has been found that the normal higher alkyl benzene para sulfonates, particularly the sodium salts thereof, possess the unusual property of strongly resembling soap in many of these physical characteristics while still being essentially of the washing power of synthetic detergents. These alkyl aryl sulfonates can be combined with minor amounts of emulsifiable plasticizers to make excellent bar products, much resembling soaps. Other synthetic detergents can also be made into useful :bar products with the assistance of plasticiziing or bodying ingredients. Without the addition of modifying non-detergent compounds, only rarely can a synthetic detergent be manufactured in suitable milled and plodded bar form.

The subject invention is based on the surprising discovery that an effective detergent bar can be milled and plodded, without tending to crack either during or after the making of the bar by means of the combination of certain synthetic detergents as hereinafter defined, in certain prescribed proportions, in the absence of a plasticlzer.

According to this invention, a milled and plodded synthetic detergent bar consists essentially of water soluble synthetic anionic organic non soap detergent, of which a major proportion of the anionic organic nonsoap detergent, up to percent by weight, is a water soluble normal higher alkyl sulfonate in which the normal alkyl group is of 15 to 20 carbon atoms, having an average chain length of 17 to 18 carbon atoms, and 5-30 percent by weight of the anionic organic non-soap detergent, is a water soluble straight chain alkyl aryl sulfonate in which the straight chain alkyl group is of 8 to 20 carbon atoms, having an average chain length of 12 to 16 carbon atoms,-said combination of detergents forming a cohesive milled and plodded toilet bar having soap-like characteristics in the absence of a plasticizer.

That such a combination of detergents would have the specific properties required to make a satisfactory detergent bar without the necessity for inclusion therein of substantial proportions of soap, or builders, and free of plasticizers is surprising and unusual, especially in view of the fact that experimentation on bars made from the individual components of the invention has indicated that when used alone they are unsuitable for use. Nevertheless, in combination a new product has been formed possessing unexpectedly beneficial properties unlike those of its constituents. A further beneficial property is that the particular combination of detergents employed in the bars of this invention are biodegradable.

Normal alkyl sulfonates employed are, as is evident from the name, compounds in which the alkyl group has a sulfonic acid radical joined to a terminal carbon atom. In addition, the alkyl group is of straight chain configuration, not of a branched or ramified structure. The alkyl radical may be of 15 to 20 carbon atoms, from pentadecyl to eicosanyl; the average chain length of any mixture of such radicals employed should be within the range of 17 to 18 carbon atoms. The salts atoms.

solubility rate of the bar. .sition also has excellent cleaning powers, is of approximately neutral pH and mild in its action on the skin, and

of the n-a-llcyl sulfonic acid are usually and preferably employed in mixture.

The straight chain terminally sulfonated alkanes may be made by reacting a free radical, obtained from ammonium bisulfite, with 1-olefin, removing unreacted hydrocarbons and then neutralizing the sulfonic acid with a suitable base, e.g., sodium hydroxide. The solution remaining may be dried or it may be combined with other detergents in the crutcher followed by drying of the en tire composition.

Many of the alkyl sulfonates that have been on the market for several years are not of the type described above. Although some of these compounds have been referred to as straight chain alkyl sulfonates the sulfonic group thereof was not terminally located. Consequently, these'older materials did not possess the properties of the normal alkyl sulfonates which make them useful in the present compositions. If the n-alkyl sulfonates were replaced by more highly branched alkyl sul-fonates the de- -tergent product resulting from the composition of such branched compound and alkyl aryl sul-fonate would be -more difiicult to process and would not have the outstanding product characteristics of the present composition.

Alkyl a-ryl sulfonates of the invented compositions are straight chain alkyl benzene sulfonates in which the normal alkyl radical is of 8 to 20 carbon atoms, ave-raging 12 to 16 carbon atoms.

These detergents are used in the forms of their water soluble salts. The salt-forming cations may he alkali metals, alkaline earth metals or triethanolamine. The normal alkyl radical may be joined to the benzene ring at a secondary carbon atom. Such alkyl benzene sul-fonates may also have the sulfonated benzene ring randomly distributed along the alkyl chain. The alkyl benzene sulfonates may be made by various well known processes, typically, by a process wherein waxes are cracked to obtain lower olefins, and thenbenzene is alkylated with these olefins, followed by sulfonation and neutralization. Such process avoids the characteristic kerosene odor sometimes found in these detergents.

In the most preferred embodiments of this invention there is also included a minor proportion of a water solub-le higher fatty acid monoglyceride sulfate detergent.

In such detergent the higher fatty acyl group is of 8 to 20 carbon atoms, preferably averaging 12 to 16 carbon The acyl group is of straight chain configuration and is also that derived from substantially saturated fatty acids. The terminal hydroxyls of the monoglyceride sulfate are esterified by fatty acid and sulfuric acid while the secondary hydroxyls remain unreacted. The water soluble detergents employed in making the composition of this invention are salts of the monoglyceride sulfuric acid, the salts forming suitable cations being alakali metals, alkaline earth metals and triethanol-amine.

The monoglyceride sulfate detergent in the present preferred detergent bars coact with the normal higher alkyl sulfonte and straight chain alkyl benzene sulfonate to make a composition of improvedfoaming properties which also reveals no undispersed curd in the wash water. These advantages are obtained without an increase in the The three detergent compocan be readily and economically manufactured in the usual soap=making equipment.

To the above formulas there may be added a minor proportion of higher fatty acid of 16 to 22 carbon atoms. The fatty acid, which is preferably all saturated fatty acid, eg stearic acid, has an emollient effect in the described composition. Such fatty acid also has the benefits of helping to regulate the solubility rate of the detengent bar and promotes formation of a creamy lather. The presence of such fatty acid will also contribute an additional waxy or soap-like surf-ace appearance to the bar product.

To obtain the special benefits of the combination of detergents of this invention, it is essential that the correct proportions of detergents must be employed. The total of synthetic organic detergents present, all of which are anionic detergents, should he 75 percent or more of the anhydrous or dry composition. All parts given in this specification and in the claims are by weight and all proportions or percentages are on a dry basis except for moisture, which is calculated on an as is or as re .ceived basis. Of the synthetic detergent a major proportion up to percent thereof, must be higher n-alky sulfonate and from 5 to 30 percent must be straight chain higher alkyl benzene sulfonate. The amount of monoglyceride sulfate, when present, may be from 2 to 20 percent of the synthetic detergent, less than 2 percent of such detergent having insulficient apparent effect on the composition. Other compatible synthetic detergents may also he added such as the higher fatty alcohol sulfates, e.g., tallow alcohol sulfate, higher fatty acid lower alkylolamide sulfates, e.g., myristic isopropanolamide sulfate, the su-lfated ethoxylated alkyl phenols, e.g., nonyl phenol ethoxylated with 5 moles ethylene oxide, sulfated and neutralized to the sodium salt, higher acyl amides of ability and to improve other desirable product and processi-ng characteristics and may also be used in certain measure to regulate or minimize properties such as solubility and s'loughing.

The proportions of detergents in the most preferred embodiments of this invention known at the present, on the dry basis are 50-70 percent n-higher alkyl sulfonate, 10-25 percent straight chain higher alkyl benzene sulfonate and 2-15 percent higher fatty monoglyceride sulfate.

The synthetic detergents which make up the bar compositions of this invention are preferably used in the forms of their sodium salts. Other cations forming water soluble products may be substituted for sodium, magnesium and potassium being especially useful in this respect. However, to promote most efiicient processing and to result in a product of satisfactory balanced properties the major proportion of detergent present should he as salts of sodium. It will be appreciated that when the detergents are mixed together in an aqueous medium there might be a transfer of cations between detergents. It is thereforedesirable that the cations should be so chosen as to minimize the production of any final product in which the component detergent salts are not in correct balance, -i.e., in which the product might be un- Among the advantages of the present compositions is the unexpected complementary actions of the n-higher alkyl sulfonate and straight chain alkyl benzene sulfonate in producing a bar product of excellent detergency, with many soap-like physical characteristics. In making a bar of this composition it is not necessary to use large amounts of inorganic salt builder, fillers or special plasticizers. The amount of water soluble inorganic salt in the bars should not exceed percent of the dry composition and is preferably held to a minimum of about 5 percent or less. Of course adjuvants may be employed to give the bar specific utilitarian or aesthetic properties. Thus, bactericides, cold cream, lanolin, whitening agents, perfumes, dyes, pigments, may be added for their desired functions. Foam improvers such as the higher fatty acid lower alkylol-amides, e.g., lauric-myristic diethanolamide, and higher fatty alcohols such as tallow alcohol are also useful in amounts from 2 to 10 percent when it is considered advantageous to increase the foaming power or stability of foam of the detergent bar. Starch, amylopectin, alkali stable starch and other fractionated or modified starch products may be included in the detergent bar up to about 10 percent to decrease the slougbing rate. Starches also have the additional important effect of decreasing absorption of moisture by the bar when in a humid atmosphere. v

In many detergent bar formulas the presence of water is undesirable. Usually, synthetic detergent compositions containing alkyl aryl sulfonates are already soft and tacky and the addition of moisture only aggravates this condition. This is especially so when the detergent bar to be made is intended for facial or bath use where the bar composition should be devoid of substantial amounts of harsh inorganic salts, fillers and builders. If present, these matenials would serve to harden the resulting bar and decrease the objectionable tackiness, toughness and elasticity of the branched or centrally phenylated straight chain alkyl aryl sulfonate detergent. In the present compositions despite the presence of alkyl aryl sulfonate, the specified n-higher alkyl sulfonate-alkyl benzene sulfonate combination is not objectionably soft or tacky and can be processed into excellent detergent bars even in the presence of considerable amount of moisture. It has been unexpectedly found that the amount of water in the detergent bars of the present invention may be from about 5 to by weight of the final bar weight and that such high amounts of water facilitate milling and plodding without any loss in desirable physical properties. The proportion of water that will be utilized is determined in large measure by the properties of the detergent formula being processed, the operator usually adding enough moisture prior to milling so that the milled chips and plodded bars will process readily. It is-apparent, however, that the ability of the instant bars to include amounts of water in ex- "modifications as are dictated by the nature of the different materials being used. In typical manufacturing procedures the detergents in solution or slurry form, as they are obtained after neutralization, are blended together in a crutcher or other suitable mixing device. It is pre-' ferred to use aqueous solutions of detergents but dry products may also be blended into an aqueous medium in the crutcher. Following the addition of the detergent components, in any suitable order, there are added the various other constituents which are heat stable and do not deteriorate in the aqueous medium in the presence of other components of the finished product. Thus, higher fatty acid, starch, fatty alcohol and alkylolamides may be added at this step. After crutching to homogeneity, the crutcher mix is dried, preferably in a moving film, plate or drum drier in which the period of maintenance at elevated temperature is relatively small. In the drier the moisture content of the mix is lowered from 40 to 70 percent to about 5 to percent. If insuificiently dried, the partially dried product may then be subjected to another dehydrating operation such as passage through the conventional hot air tunnel drier used for soap manufacture. The resulting detergent composition, in solid form, preferably as a film, ribbon or sheet, is then amalgamated with adjuvants, milled into ribbon form, plodded, pressed, wrapped and packed in the manner conventional in the soap-making industry. Instead of utilizing the crutcher as the primary mixing and reaction vessel the various dry detergents and other materials may be compounded in the malgamator but this process has the dis advantages of generating detergent dust and resulting in a product which sometimes contains small specks of unblended ingredients that give the bar an objectionable sandy feeling. The following examples are illustrative of some embodiments of the invention.

A blend of compounds of formula CHs('CH2)nCH2SO3Na, where ('CHz)n 1s aliphatic and n is 13 to 18, averaging '171S.

A blend of compounds of formula RC HiSOsNa wherein R is a straight chain of 8 to 20 carbon atoms, averaging about '1 2, and is oined to the phenyl group at any secondary posi tron along 'the chain.

The sodium salt derived from hydrogenated coconut oil.

The alkyl sulfonate, alkyl benzene sulfonate, monoglyceride sulfate, stearic acid were mixed as a slurry containing approximately 40 percent solids and 60 percent water. A portion of solids was sodium sulfate, present as a minor impurity with the organic detergents. The slurry was mixed for approximately /2 hour at F. after which it was drum dried, milled, plodded and pressed into bars, analyzing 8 percent moisture. The minor adjuvants such as perfume, bactericide, brightener, color and some water were added to the dried chips in an amalgamation step preceding milling. This composition milled and plodded much like fatty acid soap and was readily pressed into bar form by automatic machinery. The finished bar was hard, like soap, possessed a good gloss, took the imprint of lettering and designs very well and in short was of excellent appearance.

When evaluated for lathering power in a standard sponge lather testing machine the results indicated that the bars were very quick to foam, taking less than /6 the number of strokes required by a standard soap bar to form a satisfactory stable foam in hard water. Such excellent foaming was obtained with a product which had a solubility rate which was satisfactorily low for an allsynthetic detergent composition. Evaluators found that the bar rinsed very well and left the skin feeling soft, not tight and dry or sticky as is the case with many synthetic detergents. It was also established that this bar had the unusual property of absorbing very little moisture from a humid atmosphere, avoiding sweating problems and promoting dimensional stability and constant satisfactory surface appearance during use and storage. The pH of a 1 percent solution of the above bar composition was in the range of 6 to 8, and most of these bars had a pH around 6.5. It is an aim in the manufacture of detergent bars to produce a stable product such as this one at a pH approximating neutrality rather than alkalinity, which is objectionable to sensitive skin or acidity, which tends to adversely affect the detergents and adjuvants employed.

Bar compositions in which the detergent employed did not include mixtures of the alkyl sulfonate and alkyl benzene sulfonate at the critical levels hereinbefore set forth, were found to be substantially deficient compared to the product of this example and so are considered unsatisfactory. Similarly, only the .alkyl sulfonate salts listed in the specification were useful, even the ammonium salts thereof being of a serious degree of instability and secondary alkyl sulfonates being incapable of making satisfactory bars including the alkyl benzene sulfonate.

Example 2 Percent Mixed n-alkane sodium sulfonate 1 58.0 Mixed straight chain higher alkyl benzene sodium Contains approximately equal proportions of normal alkyl radicals of from 15 to 20 carbon atoms, average chain length being 17-18.

2 Mixed p-, oand m-sulfcna-tes wherein the alkyl radloals are mixed alkyls of to carbon atoms, averaging about 12 carbon atoms and are randomly joined to the benzene ring at a plurality of positions from 2-carbon -to S-carbon.

The above bar was easily made according to the procedure of Example 1. It processed excellently and the prodnot made was a superior all-detergent bar of excellent appearance and use characteristics. Good solubility, excellent foam, mild pH (6.6), excellent. rinsability, low atmospheric moisture absorption and acceptable sloughing characterized this product. It also is outstanding because it leaves the skin feeling-soft and refreshed after washing, not tight and dry as do many other detergents.

When potassium, magnesium, calcium or triethanolamine salts of the detergents are used instead of part of the sodium salts illustrated, products of similar characteristics are obtained.

1A blend of compounds of formula CHs(CH2)n( JH2SOsNa, where ('CH2)I! is aliphatic and n is 1-3 to 18. averaging 1718.

Predominantly para-sulfonated randomly alkylated benzene, the alkyl radical averaging 12 to 15 carbon atoms.

3 Lauric-myristic diethanolamide.

Bars of this composition were made according to the procedure of Example 1. Evaluations of the product showed it to be a useful detergent bar of good appearance, mild (pH of 7.7), excellent foaming power and rinsability and having other desirable properties of a good detergent bar although not being of the same general superiority as the bars of previous examples.

Examples 4-6 A series of bars was made in which mixtures of sodium and magnesium detergents were employed. In the following table these formulas are given in parts by weight.

Example Sodium n-alkyl sulionate l 50 80 Magnesium n-alkyl sulfonate 1 30 Sodium alkyl benzene sulfonate 2O Magnesium alkyl benzene sulfonate 20 10 Moisture 9 7 5. 5

t The n-alkyl sulfonate having an alkyl group averaging 17-18 carbon a $iie alkyl being straight chain and randomly phenylated, having an average of 12 carbon atoms.

The detergents used contained minor percentages of inorganic sulfates, the magnesium detergents having magnesium sulfate and the sodium detergents containing sodium sulfate. Bars can be readily made by the method of Example 1. Such bars will foam very well despite the fact that they are somewhat less soluble than comparable bars containing only sodium detergent. Such bars will have good appearance and be of approximately neutral pH.

Example 7 Percent n-Alkyl sodium sulfona-te 1 70.5 Mixed straight chain higher alkyl benzene sodium sulfonate 2 8.4 Tallow alcohol sulfate, sodium salt 8.8 Sodium sulfate 3.5 Adjuvants (bactericide, color, perfume) 1.6 Water 7.2

. A blend of compounds of formula CHaCCHzMCH-zSOsNa,

here (CH2)n is aliphatic and 'n is 13 to 18, averaging 17- 18.

Mixed p, oand m-sulfonates wherein the alkyl radicals are mixed alkyls of 10 to 15 carbon atoms, averaging about 12 carbon atoms and are randomly joined to the benzene ring at a plurality of positions from 2-carbon rto S-carbon.

This bar wvas made according to the procedure of Example 1. Evaluation of the product showed it to be a useful detergent bar of good appearance, foaming power, and rinsability and having other desirable properties of a good detergent bar.

Example 8 Percent n-Alkyl sodium sulfonate 1 61.9 Mixed straight chain higher alkyl benzene sodium A blend of compounds of formula CHs(CH-2)nCH2SlOsN where (0112) is aliphatic and n is 13 to 18, averaging 17-18.

Mixed p-, 0- and m-sulfonates wherein the alkyl radicals are mixed alkyls of 10 to 15 carbon atoms. averaging about 12 carbon atoms and are randomly joined to the benzene ring at a plurality of positions from 2-carbon to 8-carb'on.

This bar was made according to the procedure of Example 1. Evaluation of the product showed it to be a useful detergent bar of good appearance, foaming power, and rinsability and having other desirable properties of a good detergent bar.

As will be seen from the formulas, each of these bars consists essentially of the n-alkyl sulfonate and straight chain higher alkyl benzene sulfonate, the additional detergents and adjuvants not being destructiveof the benefioial effects obtained from the combination of these two materials. a

The present invention has been illustrated by description of the invented products made and manufacturing methods employed. These examples are illustrative only and are not to be considered as limiting the allowed claims.

What is claimed is:

1. A milled and plodded synthetic detergent bar consisting essentially of water soluble synthetic anionic organic non-soap detergent, of which a major proportion of the anionic organic non-soap detergent, up to 90 percent by weight, is a water soluble normal higher alkyl sulfonate in which the normal alkyl group is of 15 to 20 carbon atoms, having an average chain length of 17 to 18 carbon atoms, and a minor proportion, -30 percent by weight of the anionic organic non-soap detergent, is -a water soluble higher straight chain alkyl aryl sulfonate in which the straight chain alkyl group is of 8 to 20 carbon atoms, having an average chain length of 12 to 16 carbon atoms and about 5 to 15 percent by weight of water, said combination of detergents forming a cohesive milled and plodded toilet bar having soap-like physical characteristics in the absence of the plasticizer.

2. A milled and plodded synthetic detergent bar consisting essentially of water soluble synthetic anionic organic non-soap detergent, of which a major proportion of the anionic organic non-soap detergent, up to 90 percent by weight, is a Water-soluble normal higher alkyl sulfonate in which the normal alkyl group is of 15 to 20 carbon atoms, having an average chain length of 17 to 18 carbon atoms, and the salt-forming cation is selected from the group consisting of alkali metals, alkaline earth metals and triethanolamide, and a minor proportion 5- 30 percent by weight of the anionic organic non-soap detergent, is a water-soluble higher straight chain alkyl aryl sulfonate in which the straight chain alkyl group [is of 8 to 20 carbon atoms, having an average chain length of 12 to 16 carbon atoms and the salt-forming cation is selected from the group consisting of alkali metals, alkaline earth metals and triethanolamine and about 5 to 15% by weight of water, said combination of detergents forming a cohesive milled and plodded toilet bar having soap-like physical characteristics in the absence of a plasticizer.

3. A milled and plodded synthetic detergent bar consisting essentially of water-soluble synthetic anionic organic non-soap detergent, of which a major proportion, up to 90 percent by weight of the synthetic anionic organic non-soap detergent, is a water-soluble normal higher alkyl sulfonate of 15 to 20 carbon atoms, having an average chain length of 17 to 18 carbon atoms, a minor proportion 5-30 percent by weight of the synthetic anionic organic non-soap detergent, is a water-soluble straight chain alkyl benzene sulfonate and another minor proportion, at least about 2 percent of the synthetic anionic organic non-soap detergent, a higher fatty acyl monoglyceride sulfate, the higher normal alkyl group of the alkyl benzene sulfonate and the higher acyl group of the monoglyceride sulfate being 8 to 20 carbon atoms and the salt-forming cations of the alkyl sulfonate, alkyl benzene sulfonate and fatty acyl monoglyceride sulfate being selected from the group consisting of alkali metals, alkaline earth metals and triethanolamine and about 5 to 15% by weight of water, said combination of detergents forming a cohesive milled and plodded toilet bar having soap-like physical characteristics in the absence of a plasticizer.

4. A milled and plodded synthetic detergent bar consisting essentially of water-soluble synthetic anionic organic non-soap detergent, of which a major proportion, up to '90 percent by weight, of the synthetic anionic organic non-soap detergent, is a water-soluble normal higher alkyl sulfonate of 15 to 20 carbon atoms, having an average chain length of 17 to 18 carbon atoms, and a minor proportion 5-30 percent by weight of the synthetic anionic organic non-soap detergent, is a water-soluble higher straight chain alkyl benzene sulfonate in which the alkyl group is of 8 to 20 carbon atoms, having an average chain length of 12 to 16 carbon atoms, the salt-forming cations of the alkyl sulfonate and alkyl benzene sulfonate being a mixture of alkali metal and alkaline earth metal and about 5 to 15 by weight of water, said combination of detergents forming a cohesive milled and plodded toilet bar having soap-like physical characteristics in the absence of a plasticizer.

5. A water-soluble milled and plodded synthetic detergent bar consisting essentially of water-soluble synthetic anionic organic non-soap detergent of which a major proportion up to percent thereof, a Water-soluble normal higher alkyl sulfonate of 15 to 20 carbon atoms, having an average chain length of 17 to 18 carbon atoms, 5 to 30 percent is a straight chain higher alkyl benzene sulfonate and 2 to 20 percent is a higher monoglyceride sulfate and alkyl benzene sulfonate and the higher acyl group of the monoglyceride ulfate being of 8 to 20 carbon atoms and averaging from 12 to 16 carbon atoms, and the saltforming cations of these detergents being selected from the group consisting of alkali metals, alkaline earth metals and triethanolamine and about 5 to 15% by weight of water, said combination of detergents forming a cohesive milled and plodded toilet bar having soap-like physical characteristics in the absence of a plasticizer.

6. A milled and plodded water-soluble synthetic organic detergent bar consisting essentially of water-soluble synthetic anionic organic non-soap detergent of which a major proportion up to 90 percent thereof, is a watersoluble normal higher alkyl sulfonate of 15 to 20 carbon atoms having an average chain length of 17 to 18 carbon atoms and 5 to 30 percent is a straight chain higher alkyl benzene sulfonate of 8 to 20 carbon atoms and averaging from 12 to 16 carbon atoms, and the salt-forming cations of these detergents being a mixture of sodium and magnesium and about 5 to 15 by weight of water, said combination of detergents forming a cohesive milled and plodded toilet bar having soap-like physical characteristics in the absence of a plasticizer.

7. A milled and plodded water-soluble synthetic organic detergent bar consisting essentially of water-soluble synthetic anionic organic non-soap detergent, of which a major proportion up to 90 percent thereof, is a watersoluble normal higher alkyl sulfonate of 15 to 20 carbon atoms having an average chain length of 17 to 18 carbon atoms, from 5 to 30 percent is a water-soluble straight chain higher alkyl benzene sulfonate and from 2 to 20 percent is a higher monoglyceride sulfate, the higher alkyl groups of the alkyl benzene sulfonate and the higher acyl group of the monoglyceride sulfate being of 8 to 20 carbon atoms and averaging from 12 to 16 carbon atoms and the salt-forming cations of these detergents being selected from'the group consisting of alkali metals, alkaline earth metals and triethanolamine; less than 10 percent of inorganic builder and filler salt; and 5 to 15 percent by weight of water, said combination of constituents forming a cohesive milled and plodded toilet bar having soap-like physical characteristics in the absence of a plasticizer.

8. A milled and plodded water-soluble synthetic organic detergent bar consisting essentially of synthetic anionic organic non-soap detergent of which 50 to 70 percent is a water-soluble normal higher aliphatic alkyl sulfonate of 15 to 20 carbon atoms having an average chain length of 17 to 18 carbon atoms, 10 to 25 percent is a straight chain higher alkyl benzene sulfonate and from 2 to 15 percent is a higher monoglyceride sulfate,

the higher alkyl groups of alkyl benzene sulfonate and the higher acyl group of monoglyceride sulfate being of 8 to 20 carbon atoms and averaging from 12 to 16 carbon atoms and the salt-forming cation of these detergents being sodium; less than 10 percent inorganic builder and filler salt; and 5 to 15 percent by weight of Water; all the above constituents being homogeneously distributed throughout the detergent bar, and said combination of constituents forming a cohesive milled and plodded toilet bar having soap-like physical characteristics in the absence of a plasticizer.

ganic detergent bar comprising about 64 percent sodium normal higher alkyl' sulfonate, the normal alkyl group thereof being of about 15 to 20 carbon atoms and averaging about 17-18 carbon atoms, 17 percent sodium higher straight chain alkyl benzene sulfonate, the straight chain alkyl group of which contains 8 to 20 carbon atoms, averaging 12 carbon atoms and 4 percent sodium higher fatty monoglyceride sulfate, the acyl group of which is derived from hydrogenated coconut oil; less than 10 percent water-soluble inorganic builder and filler salt; and 8 percent by Weight of Water; all the above constituents being homogeneously distributed throughout the detergent bar, and said combination of constituent forming a References Cited by the Examiner UNITED STATES PATENTS Flett 252-161 Harman 252-161 Van Dijck et a1 252-161 Turck 252-161 Mayhew et a1 252-161 Geitz 252-16 1 Hewitt 252-161 Clippinger 252-161 Sweeney 252-161 SAMUEL H. BLECH, Primary Examiner.

cohesive milled and plodcled toilet bar having soap-like 15 ALBERT MEYERS Examiner physical characteristics in the absence of a plasticizer.

I. GLUCK, Assistant Examiner. 

1. A MILLED AND PLODDED SYNTHETIC DETERGENT BAR CONSISTING ESSENTIALLY OF WATER SOLUBLE SYNTHETIC ANIONIC ORGANIC NON-SOAP DETERGENT, OF WHICH A MAJOR PROPORTION OF THE ANIONIC ORGANIC NON-SOAP DETERGENT, UP TO 90 PERCENT BY WEIGHT, IS A WATER SOLUBLE NORMAL HIGHER ALKYL SULFONATE IN WHICH THE NORMAL ALKYL GROUP IS OF 15 TO 20 CARBON ATOMS, HAVING AN AVERAGE CHAIN LENGTH OF 17 TO 18 CARBON ATOMS, AND A MINOR PROPORTION, 5-30 PERCENT BY WEIGHT OF THE ANIONIC ORGANIC NON-SOAP DETERGENT, IS A WATER SOLUBLE HIGHER STRAIGHT CHAIN ALKYL ARYL SULFONATE IN WHICH THE STRAIGHT CHAIN ALKYL GROUP IS OF 8 TO 20 CARBON ATOMS, HAVING AN AVERAGE CHAIN LENGTH OF 12 TO 16 CARBON ATOMS AND ABOUT 5 TO 15 PERCENT BY WEIGHT OF WATER, SAID COMBINATION OF DETERGENTS FORMING A COHESIVE MILLED AND PLODDED TOILET BAR HAVING SOAP-LIKE PHYSICAL CHARACTERISTICS IN THE ABSENCE OF THE PLASTICIZER. 